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Introduction:
Cubic equation of state is very important in process calculations particularly in the oil and
gas industries. Since the first cubic equation of state (EoS) in 1873 by van der Waals, many
improved versions of two-parameter equation of state have been proposed. The obvious
drawback of fixed critical compressibility factors and certain other problems led to development of
three-parameter cubic equation of state. The addition of one more parameter provides flexibility
and hence improves the performance, but its application to heavy hydrocarbons results in large
error. Particularly, the liquid density prediction for higher carbon number components with
available equations is challenging. The proposed three-parameter cubic equation of state for pure
non-hydrocarbons and hydrocarbons commonly found in heavy oils is the basic work aimed at
PVT modeling of heavy oils.
Commonly used equations such as Soave- Redlich- Kwong (SRK) and Peng- Robinson
(PR) suffer from limitations which make them unsuitable for heavy oils or heavy hydrocarbon
components. These two equations are often used with Peneloux volume shift (Peneloux et al.
1982) to predict liquid density. Equations of volume shift (Mathias et al., 1989, Monnery et al.,
1998, Sant Ana et al., 1999) require two or three additional parameters for each component,
which are often found experimentally. Also, application of volume shift does not improve the
phase behaviour prediction.
Inclusion of third parameter in cubic equation of state allows flexibility and hence provides
better results compared to two parameter equation of state. But not all the three parameter cubic
equations of state perform equally well. General form of three parameter cubic equation of state
is given as:
( ) 1
=
+
Major three-parameter cubic equations have and as functions of acentric factor and
both increase with increasing acentric factor. Harmens and Knapp, 1980 has two brackets for
( ) and has not been tried with heavy components. Application of this equation for heavy
hydrocarbon liquid density prediction results in increasing error with increase in carbon number.
Patel and Teja, 1981 (PT EoS) proposed three parameter cubic equation of state, formulation of
which is not simple but saturated liquid density and vapour pressure prediction for hydrocarbons
is good. Though, for lighter hydrocarbons (< n-Nonane), saturated liquid density prediction error
is around 4%, for heavier (upto n-Eicosane) the error is reported to be less than 1%. As, we will
see later that application of this equation for density prediction at pressure-temperature points
other than saturation area also results in increasing error with increase in carbon number.
Volume Translated Peng-Robinson (VTPR) equations are another form of three
parameter cubic equations of state. Equation proposed by Sheng et al. 1990 considers ( ) and
in general form of cubic EoS as function of reduced temperature and there are seven
component specific coefficients (A1, A2, A3, u0, u1, u2, and u3). Later work by Tsai and Chen
(1998) on VTPR is extensive, but it has added more complexity by making ( ) and transfer
parameter (t) a function of reduced temperature. Correlations for coefficients (M, K1, and K2)
used in this VTPR equations are of 4th degree and also other parameters (N, K3) are component
specific. Hence, VTPR equations are very complex and not user friendly.
In view of above review, our goal is to develop a three parameter cubic equation of state
having simplicity of PR EoS (except the addition of one more parameter), but predicts liquid
density with minimum error. In the proposed work, commonly found associated non-hydrocarbons
such as N2, CO2, H2S and 30 hydrocarbons (highest being C40H82) were used to model the
different parameters. The proposed equation has been developed in line with PR equation of
state, offering least complication unlike many other three-parameter equations of state. It is
observed that the proposed equation maintains consistency with an average absolute error of
2.5%. Similar trend is also observed in the prediction of the saturated liquid density and vapour
pressure prediction.
= 3
( )
In ( , ), is the molar volume and is a constant related to the size of the hard spheres. The
parameter a( ) takes into account the intermolecular attraction force. A common form of ( , )
is given as:
( , )= + 5
Here u is function of the acentric factor of the compound and w is the function of u. The
parameter a(T) is the product of ac and (T), where ac is value of a(T) at the critical point and
(T) is function of the reduced temperature, such that it is unity at critical point.
a( ) = ( ) 6
= 7
( ) +
Taking the first partial derivative of with respect to , keeping constant, and imposing it at the
critical point gives:
[2 + ] 8
=
( ) [ + ]
Taking the second partial derivative of with respect to , keeping T constant, and imposing this
on critical point gives:
2 [2(2 + ) 2( + )] 9
=
( ) ( + )
= 10
( ) 11
=
= 12
Parameters and are functions of u, w, and . Actual expressions (listed in
appendix) for , , and are complicated, however user friendly forms for these with negligible
weighted (with respect to u) % absolute deviation of 0.15, 0.05, and 0.013 respectively, are
presented in the following equations:
= 13
0.2294 + 0.15037 0.005211
= 14
2.2727+ 11.5807 6.5737
0.014728 15
= 0.006488 + + 0.423
Parameters and has been modelled keeping in view following two factors:
1. ( , ) increases with increasing acentric factor. Unlike many three parameter cubic
equations of state where difference of parameters and is held constant, In the present
work this difference increases with increasing acentric factor, by making decrease with
increasing .
2. decreases with increasing acentric factor and remains almost equal to of PR EoS.
With the proposed equation average % absolute deviation for from of PR EoS (i.e.
0.45724) is 0.5%. However, decreases till acentric factor of 0.6 and after that there is
increase with small gradient.
Parameters and were obtained from best fit over a wide range of experimental data
in two steps. At step one, starting with initial assumption for (Equation 26), best value of was
obtained for each component giving minimum error for experimental PVT data, keeping the
critical compressibility close to experimental one. A correlation was thus obtained for , which
was used to obtain as function of acentric factor from experimental vapor pressure data at
second step. This was again used at step 1 to find suitable correlation for . This was
continued until optimum minimum % average absolute error was obtained for each component.
= 19
a( ) 20
=
( )
= 21
with:
( ) ( ) 24
=
The expression for ( ) is same as used in SRK and PR EoS, and given as:
.
25
( )= 1+ 1
The vapour pressure calculation using the equation 1, was done for 27 components and
the value for m was tuned to give least deviation from experimental data. Optimum values were
then correlated with the acentric factor to give following relation (Figure 1):
= 0.3547 + 1.6296 0.2773 26
2
Octacosane
1.8 m = -0.2773 2 + 1.6296 + 0.3547 Docosane
R = 0.9998 Nonadecane Tetracosane
1.6
Eicosane
Hexadecane
1.4 Octadecane
Tetradecane
1.2 Dodecane
1 Decane
m
Pentane Nonane
Octane
0.8 Cyclo Hexane Heptane
Iso Butane Hexane
0.6 Propyelene CO2
Ethylene Butane Benzene
0.4 Propane
H2S
Nitrogen Ethane
0.2 Methane
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Acentric Factor,
= 27
.
= (1 , ) 28
29
=
30
=
+( 1) +( ) +( + )=0 31
( 1) 2 32
log = log( )+ , + , where
( +4 )
= ( ) ( 2 ) 1
( )
+( ) (2 + ) 1
( )
2
2 + 2 +4
= log
2 +4 2 + + 2 +4
Proposed mixing rules for u and w (Equation 29 & 30) result in marginal improved result over the
linear mixing rule. However, these mixing rules are presented here as they have been used for
heavy oils and perform better than other mixing rules.
Comparison of Calculations:
The proposed equation of state is developed for hydrocarbon components and
associated non-hydrocarbons commonly found in oil and gas reservoirs. In this study, 34
compounds were considered among which 30 components were hydrocarbons. The highest
carbon number hydrocarbon investigated is n-Tetracontane (C40H82). Except for N2 and CO, liquid
density data for rest of the components were used. Vapour pressure, corresponding liquid and
vapour density predictions for 19 components were investigated considering two prominent two
parameter equation of state, SRK and PR EoS and one three parameter cubic equation of state
often used, Patel and Teja, 1981 (PT EoS). VTPR EoS was not included in the comparison as
they require several parameters which make them complex and also, some parameters are
component specific.
It is obvious from the comparison that for all components, the predicted saturated liquid
density is much better than SRK and PR equations. For PT EoS for lighter components the error
is marginally higher than the proposed equation, for higher hydrocarbons it is almost equal.
Keeping in view the trends of error, the proposed equation should produce saturated liquid
density within 2.5% deviation even for higher hydrocarbons.
Saturated Vapour Density Calculation:
The saturated vapour density was calculated for all compounds considered for the vapour
pressure calculation. The comparison is presented in Table 5. Though, the SRK EoS appears
performing consistently well, on average the error for the proposed equation is a little higher than
that of the SRK and slightly better than that of the PR EoS. The proposed equation, on average
predicts better results compared to PT EoS.
Conclusion:
From the comparison, it is evident that the proposed equation can predict liquid density in
general, and the saturated liquid density with an average absolute error less than 2.5%, whereas
with other equations of state, the error in prediction keeps on increasing with increasing carbon
number. Deviation in vapour pressure prediction with the proposed equation is also better than
other equation. Vapour density prediction is slightly better than PR EoS and close to SRK
equation. Enthalpy departure prediction is better than SRK, and close to PR and PT EoS. Given
a significantly better liquid density prediction, better enthalpy departure prediction for higher
hydrocarbons is also expected.
It is important to note that error with the proposed equation for all predicted
thermodynamic parameters is consistent and very low, whereas for the other equations, there is
an increasing trend and for higher hydrocarbon, errors can be very high. This makes the
proposed equation suitable for PVT prediction for pure and mixed hydrocarbons and non-
hydrocarbons associated with crude oil.
Acknowledgement: The authors thank Petroleum Technology Research Centre, Regina, SK,
Canada, for the financial support provided for this project.
Appendix
Actual expression for , , :
( 1) 4 + ( 2 + ( )+ + 2) ( 1)
= + + +1
2 2
( 1) 4 + ( 2 + ( )+ + 2)
+
2 2
( 2 + )
=
(2 + )( 1)
( 2 + )[ + ]
=
[(2 + )( 1) ]
2.0736 + 0.000655
=
298.02
1 + 0.0006867
M is molecular weight
0.003784 0.01474
=
1 + 0.0004109 + 7.4913 10
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